化合物4淡黃色油狀物;[α]21.7D -27.1(c 0.27,MeOH),ESI-MS m/z 233[M+Na]+。1H-NMR(CDCl3,400 MHz)δ:3.91(1H,m,H-3),2.45(2H,br s,H-8),2.25(2H,br s,H-7),2.13(3H,s,H-10),1.91(2H,m,H-4),1.67(1H,m,H-2b),1.58(3H,s,H-13),1.37(1H,m,H-2a),1.02(3H,s,H-11),1.00(3H,s,H-12);13C-NMR(CDC13,100 MHz)。以上數據與文獻[17-18]的報道一致,故鑒定該化合物為3S-3-hydroxy-7,8-dihydro-β-ionone。
化合物5淡黃色油狀物;[α]21.1D -69.8(c 0.20,MeOH),ESI-MS m/z 247[M+Na]+。1H-NMR(CDC13,400 MHz)δ:7.06(1H,d,J=15.8 Hz,H-7),6.27(1H,d,J=15.8 Hz,H-8),3.89(1H,m,H-3),2.37(1H,dd,J=14.1,1.7 Hz,H-4a),2.36(3H,s,H-10),1.65(1H,dd,J=14.1,9.0 Hz,H-4b),1.61(1H,dd,J=12.7,1.7 Hz,H-2a),1.25(1H,dd,J=12.7,10.7 Hz,H-2b),1.18(3H,s,H-13),1.17(3H,s,H-12),0.97(3H,s,H-11);13C-NMR(CDC13,100 MHz)。以上數據與文獻[19-21]的報道一致,故鑒定該化合物為(3S,5R,6S)-3-hydroxy-5,6-epoxy-β-ionone。
化合物6淡黃色油狀物;[α]21.1D+9.8(c 0.20,MeOH),ESI-MS m/z 233[M+Na]+。1H-NMR(CDCl3,400 MHz)δ:5.80(1H,s,H-4),3.82(1H,m,H-9),2.48(1H,d,J = 16.9 Hz,H-2b),1.98(1H,d,J=16.9 Hz,H-2a),1.97(1H,m,H-6),1.81(1H,m,H-7b),1.68(1H,m,H-8b),1.67(1H,m,H-7a),1.61(1H,m,H-8a),1.25(3H,d,J=6.3 Hz,H-10),1.07(3H,s,H-13),1.02(3H,s,H-12),1.09(3H,s,H-11);13C-NMR(CDCl3,100 MHz)。以上數據與文獻[22]的報道一致,故鑒定該化合物為(6R,9R)-9-hydroxy-4-megastigmen-3-one。
化合物7黃色油狀物;[α]21.2D -49.9(c 0.62,MeOH),ESI-MS m/z 247[M+Na]+。1H-NMR(CD3OD,400 MHz)δ:5.83(1H,s,H-8),4.21(1H,m,H-3),2.17(1H,m,H-4a),1.93(1H,m,H-2a),1.39(1H,m,H-2b),1.38(1H,m,H-4b),2.19,1.40,1.40,1.15(各3H,-CH3×4);13C-NMR(CD3OD,100 MHz)。以上數據與文獻[23-24]的報道一致,故鑒定該化合物為(3S,5R)-dihydroxy-6,7-megstigmadien-9-one。
化合物8淡黃色油狀物;[α]21.3D -66.8(c 0.18,MeOH),EI-MS m/z 196(M+·)。1H-NMR(CDCl3,400 MHz)δ:5.70(1H,s,H-7),4.34(1H,d,J=3.7 Hz,H-3),2.48(1H,dt,J=13.9,2.6 Hz,H-4b),2.00(1H,dt,J=14.6,2.6 Hz,H-2b),1.80(1H,dd,J = 13.9,4.0 Hz,H-4a),1.79(3H,s,H-11),1.54(1H,dd,J=14.6,3.7 Hz,H-2a),1.48(3H,s,H-10),1.28(3H,s,H-9);13C-NMR(CDC13,100 MHz)。以上數據與文獻[25]的報道一致,故鑒定該化合物為(-)-loliolide。
化合物9淡黃色油狀物;[α]21.1D -4.2(c 0.22,MeOH),ESI-MS m/z 261[M+Na]+。1H-NMR(CD3OD,400 MHz)δ:3.37(1H,m,H-9),2.42(1H,ddd,J=11.4,7.5,4.2 Hz,H-2),1.94(1H,m,H-11a),1.80(1H,m,H-10b),1.79(1H,m,H-3b),1.78(1H,m,H-12a),1.77(1H,m,H-5),1.63(1H,m,H-10a),1.57(1H,m,H-3a),1.45(1H,m,H-7b),1.38(2H,m,H-6),1.37(1H,br d,J=13.6 Hz,H-12b),1.29(1H,m,H-11b),1.12(3H,s,H-14),1.03(1H,dd,J=13.9,12.6 Hz,H-7a),0.94(3H,s,H-15),0.87(3H,s,H-13);13C-NMR(CD3OD,100 MHz)。以上數據與文獻[26]的報道一致,故鑒定該化合物為caryolane-1,9α-diol。
化合物10淡黃色油狀物;[α]21.1D -2.7(c 0.20,MeOH),ESI-MS m/z 259[M+Na]+。1H-NMR(CDCl3,400 MHz)δ:5.59(1H,d,J=15.9 Hz,H-10),5.55(1H,s,H-12a),5.45(1H,m,H-9),5.30(1H,s,H-13a),5.04(1H,s,H-12b),5.03(1H,s,H-13a),4.38(1H,dd, J=8.9,4.7 Hz,H-6),4.35(1H,s,H-2),3.23(1H,dd,J=13.8,7.8 Hz,H-8a),2.81(1H,dd,J=13.8,8.4 Hz,H-8b),2.27(2H,m,H-4),2.16(1H,m,H-5a),2.00(1H,dd,J=14.0,5.4 Hz,H-1a),1.93(1H,m,H-5b),1.88(1H,dd,J=14.0,2.1 Hz,H-1b),1.09(3H,s,H-14),1.01(3H,s,H-15);13C-NMR(CDCl3,100 MHz)。以上數據與文獻[27]的報道一致,故鑒定該化合物為2,6-dihydroxyhumula-3(12),7(13),9(E)-triene。
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